WO2000058709A1 - Procede et appareil permettant de determiner une caracteristique physique ou chimique d'un liquide - Google Patents

Procede et appareil permettant de determiner une caracteristique physique ou chimique d'un liquide Download PDF

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Publication number
WO2000058709A1
WO2000058709A1 PCT/GB2000/001243 GB0001243W WO0058709A1 WO 2000058709 A1 WO2000058709 A1 WO 2000058709A1 GB 0001243 W GB0001243 W GB 0001243W WO 0058709 A1 WO0058709 A1 WO 0058709A1
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WO
WIPO (PCT)
Prior art keywords
liquid
crystal
signal output
evaporation
characteristic
Prior art date
Application number
PCT/GB2000/001243
Other languages
English (en)
Inventor
Simon Nigel Port
Malcolm John Joyce
Dean Christopher Ash
Original Assignee
British Nuclear Fuels Plc
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by British Nuclear Fuels Plc filed Critical British Nuclear Fuels Plc
Priority to GB0123512A priority Critical patent/GB2363461A/en
Priority to AU35688/00A priority patent/AU3568800A/en
Publication of WO2000058709A1 publication Critical patent/WO2000058709A1/fr

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Classifications

    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01G—WEIGHING
    • G01G3/00—Weighing apparatus characterised by the use of elastically-deformable members, e.g. spring balances
    • G01G3/12—Weighing apparatus characterised by the use of elastically-deformable members, e.g. spring balances wherein the weighing element is in the form of a solid body stressed by pressure or tension during weighing
    • G01G3/13—Weighing apparatus characterised by the use of elastically-deformable members, e.g. spring balances wherein the weighing element is in the form of a solid body stressed by pressure or tension during weighing having piezoelectric or piezoresistive properties
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N11/00—Investigating flow properties of materials, e.g. viscosity, plasticity; Analysing materials by determining flow properties
    • G01N11/10—Investigating flow properties of materials, e.g. viscosity, plasticity; Analysing materials by determining flow properties by moving a body within the material
    • G01N11/16—Investigating flow properties of materials, e.g. viscosity, plasticity; Analysing materials by determining flow properties by moving a body within the material by measuring damping effect upon oscillatory body
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N5/00—Analysing materials by weighing, e.g. weighing small particles separated from a gas or liquid
    • G01N5/04—Analysing materials by weighing, e.g. weighing small particles separated from a gas or liquid by removing a component, e.g. by evaporation, and weighing the remainder

Definitions

  • the present invention relates to the determination of the characteristics of a liquid in particular by using a quartz crystal microbalance (QCM).
  • the characteristics may be. for instance, the chemical composition or the viscosity of the liquid. 5
  • the QCM was first used as an accurate weight measurement device for measuring the weight of thin film metals.
  • the microbalance works by applying an oscillating electric field across a quartz crystal.
  • the field causes a shear oscillation in the crystal known as the converse piezoelectric effect and the crystal oscillates at a stable
  • the resonant frequency of the crystal is sensitive to matter deposited on its surface or which is coupled to the surface by viscoelastic means.
  • admittance, quality factor Q, phase and radio frequency (rf) when connected to a network analyser, admittance, quality factor Q, phase and radio frequency (rf)
  • the change in mass per unit surface area comprising: depositing said liquid on a surface of a crystal of a quartz microbalance to form a droplet on said surface; evaporating said liquid from said surface; measuring a signal output of the crystal microbalance; and analysing of the signal output to determine said characteristic of said liquid.
  • the droplet on the surface of the crystal may be described as a sessile body of liquid, indicating that it simply sits on the crystal surface.
  • the characteristic of the liquid may be, for instance, some aspect of the chemical composition of the fluid or its viscosity.
  • Evaporation of the liquid drop produces changes in a number of measurable physical characteristics of the crystal any of which may be measured as a signal output from the crystal.
  • the measured values are characteristic of the chemical composition of the liquid.
  • the droplet preferably has a volume of from 0.5 to 1 ⁇ l, more preferably about 1 ⁇ l.
  • the output signal is dependant on the evaporation rate of liquid from the crystal surface.
  • the change in resonant frequency ( ⁇ / 0 ) is measured.
  • Af 0 can be measured by including the crystal microbalance as a component in an oscillator circuit.
  • any or all of the following physical characteristics namely, admittance, quality factor (Q), phase or radio frequency (rf) voltage may be measured.
  • the signal is measured as a function of time.
  • the measurements are taken at least three times per second.
  • the measurable physical characteristics may be measured using a network analyser.
  • the liquid may be composed of a single unknown chemical or a mixture of unknown chemicals.
  • the liquid may be an organic liquid.
  • the liquid mixture contains at least one organic liquid.
  • the signal output is analysed by comparing values derived from the signal output with known values contained in a database. Such a comparison allows the unknown liquid to be identified.
  • the present invention also provides an apparatus for determining a physical or chemical characteristic of a liquid, the apparatus comprising: a quartz crystal microbalance; means for depositing said liquid on the surface of said crystal microbalance to form a droplet on said surface; means for causing the evaporation of said liquid on the surface of said surface; means for measuring the signal output of the crystal microbalance; and means for analysing the signal output to determine a said characteristic of said liquid.
  • the observed frequency response is qualitatively characteristic of the specific liquid used such that a non-deterministic recognition method can be employed in order to identify the liquid.
  • the origin behind such characteristics is believed to be the variety interaction between convection and conduction processes, and the surface tension of the liquid.
  • Such liquids can be termed unstable-interface liquids.
  • the responses are generic, differing only in the severity of the response curve.
  • the response curve is parameterised by the crystal sensitivity S(r, ⁇ ), where r is the radius and ⁇ is the angle subtended from the crystal centre across its surface. This sensitivity is formally expressed as a series of Bessel functions but is more often approximated as Gaussian, as in equation (1):
  • ⁇ f max is the maximum change of frequency observed
  • r(to) is the radius of the drop at the moment it is deposited
  • v r is the retreat speed.
  • v r is defined in terms of area change per unit time
  • m 2 is used to store a database of known values.
  • a computer is used to compare the known and unknown values and select the best fit from the known signals to determine the identity of the unknown chemical.
  • the crystal is driven at its resonant frequency or harmonics thereof by an Alternating Current supply.
  • the crystal microbalance is constructed from quartz crystal.
  • the quartz crystal is unpolished.
  • the quartz crystal has a diameter of between 5mm and 15mm.
  • the quartz crystal microbalance is attached to a network analyser by means of an electrode on both its upper and lower surfaces.
  • the rate of evaporation is controllable.
  • the rate of evaporation is controlled by controlling the temperature of the crystal surface.
  • the rate of evaporation is controllable by controlling the pressure at the crystal surface.
  • the volume of liquid deposited on the surface can be controlled.
  • the method of the present invention can be used to determine the viscosity of the liquid droplet. From the Sauerbrey equation we know that the change in oscillating frequency of a Quartz crystal microbalance transducer is related to the mass loading that crystals surface (equation (1).
  • ⁇ / frequency change
  • f 0 crystal resonant frequency
  • A.m- mass change
  • A- electrode area
  • ⁇ q shear modulus of quartz
  • p q density of quartz.
  • the Sauerbrey equation assumes a solid mass loading of the crystal where the whole of the mass oscillates with the crystal frequency. As explained above, when the loading is fluid, the whole volume of the droplet will not oscillate with the crystal as the amplitude decays through the fluid.
  • the volume of fluid oscillating at the crystal frequency is equal to a volume of A* ⁇ l2.
  • This layer forms on the electrode, which acts as a solid mass and is known as the rigidly coupled layer. This layer is the ⁇ m responsible for the frequency change observed in the crystal oscillations.
  • the mass of this layer is related to the density and volume of the droplet as shown in equation (3).
  • Figure 1 shows the equipment and experimental set up used for measuring liquid characteristics on evaporation
  • Figure 2 shows a set of graphs for plotting the change in resonant frequency of the crystal against time for a range of liquids on evaporation
  • Figure 3 shows a set of graphs plotting the change in resonant frequency against time for a liquid using different types of crystal
  • Figure 4 shows a schematic diagram of a device for determining the content of a liquid
  • Figure 5 is a graph showing the change in resonant frequency against time for butan-1-ol
  • Figure 6 shows response curves for a range of alcohols
  • Figure 7 shows the results of viscosity measurements on TBP/OK mixtures.
  • a quartz crystal was used and operated at a resonant frequency of 10MHz by frequency generator 5.
  • the quartz was unpolished, with total diameter of 8mm and a silver electrode of approximately 4mm diameter on each face.
  • the crystals were connected to a network analyser 7 using grounded coaxial leads to minimise stray capacitance effects and external interference.
  • the crystal surfaces were orientated in the horizontal plane.
  • the network analyser 7 used in this work was a Hewlett Packard 8753 C and was interfaced to a personal computer 9 via Lab View, a data acquisition software package.
  • the network analyser 7 was set up to record the change in frequency ⁇ / from the resonant frequency /, at a rate of 3 measurements per second.
  • Figure 2 shows the change in resonant frequency of ⁇ f(Hz) against time for each of the above alcohols.
  • the plots (a) to (e) show the results for methanol, ethanol, propan-2-ol, butan-1-ol and pentan-1-ol, respectively.
  • the response of the oscillating quartz crystal to the dynamic loading of the evaporating alcohol is a negative pulse with a period of several minutes. Although a similar general response is exhibited by all give alcohols, each response has specific aspects that are characteristic of the alcohol used.
  • Figure 3 shows the change in resonant frequency ⁇ /(Hz) against time(s) for ethanol on three separate crystals of the same type.
  • a device 31 which can be used to determine the chemical contents of a sample.
  • a sample 32 is placed on the upper surface of a quartz crystal
  • Temperature control elements 35 are used in conjunction with a thermometer (not shown) in order to control the temperature inside the evaporation chamber 33. This in turn controls the rate of evaporation for the sample.
  • the crystal is driven by an ac signal generator 49 at the resonant frequency of the crystal (or harmonics thereof).
  • the change in frequency ⁇ is sampled by a network analyser 41 which is set to sample ⁇ /3 times per second. Sampling rate can be easily increased to improve accuracy.
  • the data obtained during sampling is then stored in a memory chip 43. Once all of the data has been collected, the stored data is downloaded onto a computer where analysis of the data is undertaken.
  • Figure 5 shows the change in resonant frequency ⁇ (Hz) against time (t) for butan-1- ol with a least squares fit to the region where the evaporation rate is constant. This linear region of the graph is due to the increase in evaporation rate being compensated for by a decrease in mass on the crystal surface. After the linear section the change in mass dominates.
  • Figure 5 has a characteristic shape similar to that of a fermi function.
  • the data of Figure 6 are the quasi-linear regions of the complete data sets. In all cases, both the early data ( lOOs), and that just prior to the crystal reaching ⁇ f ⁇ Hz, exhibit variations from the central linearity which is characteristic of radial sensitivity effects currently beyond the model used. Indeed, for methanol the linear feature between these non-linear aspects is very short due to the rapid evaporation of this alcohol.
  • the data available from measurement of the change in resonant frequency with evaporation rate can be correlated to a library of known values.
  • the measurements can be subjected to signal processing, for instance, by Fast Fourier transformation.
  • TBP tri-butyl phosphate
  • the method of the present invention may be used to measure viscosity and the viscosity values may be used to determine the percentage of odourless kerosene (OK) in TBP.
  • the measured viscosity is largely independent of the crystal used and of the droplet size. Four experiments were conducted, each with a different crystal and with no particular control of droplet size. The "actual" viscosity was also measured using a reverse flow viscometer in a constant temperature water butt.

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  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Health & Medical Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Chemical & Material Sciences (AREA)
  • Analytical Chemistry (AREA)
  • Biochemistry (AREA)
  • General Health & Medical Sciences (AREA)
  • Immunology (AREA)
  • Pathology (AREA)
  • Investigating Or Analyzing Materials By The Use Of Electric Means (AREA)
  • Sampling And Sample Adjustment (AREA)

Abstract

L'invention concerne un procédé permettant de déterminer une caractéristique physique ou chimique d'un liquide, selon lequel on place une goutte du liquide sur la surface d'un cristal d'une microbalance à quartz. On fait s'évaporer le liquide de ladite surface tandis qu'on mesure une sortie de signal de la microbalance en cristal. On analyse ensuite la sortie de signal de façon à déterminer la caractéristique du liquide, caractéristique pouvant, par exemple, être la composition chimique ou la viscosité. L'invention concerne également un appareil permettant de mettre en oeuvre le procédé de l'invention.
PCT/GB2000/001243 1999-03-31 2000-03-30 Procede et appareil permettant de determiner une caracteristique physique ou chimique d'un liquide WO2000058709A1 (fr)

Priority Applications (2)

Application Number Priority Date Filing Date Title
GB0123512A GB2363461A (en) 1999-03-31 2000-03-30 Method and apparatus for determining a physical or chemical characteristic of a liquid
AU35688/00A AU3568800A (en) 1999-03-31 2000-03-30 Method and apparatus for determining a physical or chemical characteristic of a liquid

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
GBGB9907300.9A GB9907300D0 (en) 1999-03-31 1999-03-31 Chemical sensor
GB9907300.9 1999-03-31

Publications (1)

Publication Number Publication Date
WO2000058709A1 true WO2000058709A1 (fr) 2000-10-05

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AU (1) AU3568800A (fr)
GB (2) GB9907300D0 (fr)
WO (1) WO2000058709A1 (fr)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2003066115A2 (fr) * 2002-02-04 2003-08-14 S. C. Johnson & Son, Inc. Procede et appareil pour l'evaporation de liquides a composantes multiples
US6928877B2 (en) * 2002-05-24 2005-08-16 Symyx Technologies, Inc. High throughput microbalance and methods of using same
US8215733B2 (en) * 2007-01-10 2012-07-10 Eastman Kodak Company Process and device for ink quality control
CN104713624A (zh) * 2015-03-02 2015-06-17 杭州四方称重系统有限公司 专用于车辆动态称重的石英称重传感装置及加工方法

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113640172B (zh) * 2021-08-25 2024-05-07 北京建筑大学 一种测试聚合物乳液成膜速率的装置及方法

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4788466A (en) * 1987-11-09 1988-11-29 University Of Arkansas Piezoelectric sensor Q-loss compensation
US5112642A (en) * 1990-03-30 1992-05-12 Leybold Inficon, Inc. Measuring and controlling deposition on a piezoelectric monitor crystal
WO1996035103A1 (fr) * 1995-05-04 1996-11-07 Michael Rodahl Microbalance a quartz piezo-electrique
US5734098A (en) * 1996-03-25 1998-03-31 Nalco/Exxon Energy Chemicals, L.P. Method to monitor and control chemical treatment of petroleum, petrochemical and processes with on-line quartz crystal microbalance sensors
WO1998039648A1 (fr) * 1997-03-06 1998-09-11 Alpha M.O.S. Appareil et procede de caracterisation de liquides

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4788466A (en) * 1987-11-09 1988-11-29 University Of Arkansas Piezoelectric sensor Q-loss compensation
US5112642A (en) * 1990-03-30 1992-05-12 Leybold Inficon, Inc. Measuring and controlling deposition on a piezoelectric monitor crystal
WO1996035103A1 (fr) * 1995-05-04 1996-11-07 Michael Rodahl Microbalance a quartz piezo-electrique
US5734098A (en) * 1996-03-25 1998-03-31 Nalco/Exxon Energy Chemicals, L.P. Method to monitor and control chemical treatment of petroleum, petrochemical and processes with on-line quartz crystal microbalance sensors
WO1998039648A1 (fr) * 1997-03-06 1998-09-11 Alpha M.O.S. Appareil et procede de caracterisation de liquides

Cited By (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2003066115A2 (fr) * 2002-02-04 2003-08-14 S. C. Johnson & Son, Inc. Procede et appareil pour l'evaporation de liquides a composantes multiples
WO2003066115A3 (fr) * 2002-02-04 2003-10-30 Johnson & Son Inc S C Procede et appareil pour l'evaporation de liquides a composantes multiples
US6793149B2 (en) 2002-02-04 2004-09-21 S. C. Johnson & Son, Inc. Method and apparatus for evaporating multi-component liquids
EP1502607A2 (fr) * 2002-02-04 2005-02-02 S.C. Johnson & Son, Inc. Procédé et dispositif pour tester l'aptitude d'un liquide à plusieurs composants pour l'évaporation
EP1502607A3 (fr) * 2002-02-04 2005-02-09 S.C. Johnson & Son, Inc. Procédé et dispositif pour tester l'aptitude d'un liquide à plusieurs composants pour l'évaporation
US7070121B2 (en) 2002-02-04 2006-07-04 S.C. Johnson & Son, Inc. Method and apparatus for evaporating multi-component liquids
AU2003208972B2 (en) * 2002-02-04 2008-11-06 S. C. Johnson & Son, Inc. Method and apparatus for evaporating multi-component liquids
CN100586487C (zh) * 2002-02-04 2010-02-03 约翰逊父子公司 蒸发多组分液体的方法及其装置
US6928877B2 (en) * 2002-05-24 2005-08-16 Symyx Technologies, Inc. High throughput microbalance and methods of using same
US8215733B2 (en) * 2007-01-10 2012-07-10 Eastman Kodak Company Process and device for ink quality control
CN104713624A (zh) * 2015-03-02 2015-06-17 杭州四方称重系统有限公司 专用于车辆动态称重的石英称重传感装置及加工方法

Also Published As

Publication number Publication date
GB9907300D0 (en) 1999-05-26
GB2363461A (en) 2001-12-19
AU3568800A (en) 2000-10-16
GB0123512D0 (en) 2001-11-21

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